CN102104157B - Preparation method for carbon dry gel - Google Patents
Preparation method for carbon dry gel Download PDFInfo
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- CN102104157B CN102104157B CN2009102484751A CN200910248475A CN102104157B CN 102104157 B CN102104157 B CN 102104157B CN 2009102484751 A CN2009102484751 A CN 2009102484751A CN 200910248475 A CN200910248475 A CN 200910248475A CN 102104157 B CN102104157 B CN 102104157B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a carbon carrier of a proton exchange membrane fuel cell, in particular to a preparation method for carbon dry gel. The carbon dry gel is prepared by m-dihydroxybenzene, formaldehyde and a metal salt serving as raw materials, wherein the metal salt comprises a soluble nitrate, a carbonate, a sulfate, an acetate or a halide of one or more metal elements in an IVB group, a VB group, a VIB group, a VIIB group, a VIII group, an IB group and an IIB group; the m-dihydroxybenzene serving as a precursor and the formaldehyde are in the mol ratio of 2:1; the m-dihydroxybenzene and the metal salt are in the mol ratio of 10:1-500:1; and a high-stability carbon carrier is prepared by graphitizing mixed organic carbon dry gel at the high temperature of 1,500 to 3,500 DEG C. When serving as an anti-corrosion carbon material and being used as a cathode catalyst carrier of the proton exchange membrane fuel cell, the carbon dry gel has high anti-corrosion performance and high stability in an acidic and high-potential environment of cell operation.
Description
Technical field
The present invention relates to the Proton Exchange Membrane Fuel Cells carbon carrier, a kind of preparation method of the carbon xerogel as the fuel battery cathode with proton exchange film catalyst carrier of corrosion-resistant, high stability specifically, described carbon xerogel can be used as carrier, is used for the fuel battery cathode with proton exchange film catalyst.
Background technology
Fuel cell is a kind of conversion equipment that directly chemical energy of material is converted into electric energy, is considered to the 4th class generation technology after hydroelectric power generation, thermal power generation and nuclear energy power generation.Fuel cell is not with the work of heat engine form, and the chemical energy of the most of fuel in fuel cell can directly be converted to electric energy, and power generation process is not subjected to the restriction of Carnot cycle, has higher energy conversion efficiency (40～60%).Simultaneously, produce hardly SO2, NO in the fuel cell power generation process
xWith harmful substances such as suspended matters, do not emit greenhouse gas CO2 yet, be a kind of generation mode that meets the cleaning of society environmental protection concept.Wherein particularly outstanding is hydrogen-oxygen proton exchange membrane fuel cell, and its product only has water.In application, whole fuel cell is to be in series by single battery, and the power of fuel cell can, by several watts to MW class, can use to extensive generating from mobile phone.Simultaneously, the required auxiliary equipment of fuel cell is few, and the use of almost can generating electricity anywhere, saved a large amount of power transmission lines, and convenient and reliable operation, flexibility are large.These advantages make fuel cell be acknowledged as the cleaning of 21 century first-selection, efficient generation technology, are subject in recent years the great attention of national governments and enterprise.
At present, the stability of PEMFC long-time running and expensive price are its bottlenecks of realizing the commercialization maximum, and in order further to improve the performance of PEMFC and to reduce costs, research work mainly concentrates on the improvement of eelctro-catalyst and polymer dielectric film.Material with carbon element is as the carrier of catalyst and the skeleton of porous gas diffusive electrode, and its physics and surface chemical property directly affect the performance of catalyst and whole battery.In the PEMFC operational environment, particularly under high current density, when fuel supply is deficient and after the PEMFC long-time running, the oxide etch phenomenon of carbon carrier is serious, oxidizing process can be by C+2H
2O=CO
2+ 4H
++ 4e
-(E=0.207V vs.RHE) and C+H
2O → H
2+ CO (while having Pt) expression.The corrosion of the interior carbon of battery directly causes supporting in its surperficial catalyst activity component runs off, reunites, and the metallic catalyst particle diameter increases, and active area reduces, and whole catalyst layer structure is damaged; Simultaneously, the oxide etch of material with carbon element also can affect its surperficial hydrophilicity and hydrophobicity, makes the transmission duct of reactant and product stop up.Above phenomenon finally causes battery performance decline, the useful life of PEMFC to shorten.As seen, improve the antioxidant anticorrosive performance of carbon support material, develop corrosion-resistant material with carbon element and the non-material with carbon element carrier of novel stabilising, significant for stability and the useful life of improving the PEMFC long-time running.
In recent years, the many new carbon such as carbon nano-tube, carbon nano-fiber, nano cages, charcoal gel cell catalyst carriers that act as a fuel that are similar to are applied in fuel cell, make the antioxidant anticorrosive performance of catalyst carrier that improvement to a certain degree arranged, but the performances such as pore structure, specific area remain further to be optimized.Wherein, the charcoal gel rubber material has higher electric conductivity, larger mesopore ratio, the suitable characteristics such as specific area, makes it be suitable as very much fuel-cell catalyst carrier.Simultaneously, research shows, metal-doped material can obtain the degree of graphitization higher than raw material in the same high temperature heat treatment process, reduced the preparation cost of graphitized carbon material.
Metal-doped high temperature graphitization carbon gel rubber material has good stability and corrosion resistance, and this has determined can stable existence under its high potential at Proton Exchange Membrane Fuel Cells and acid condition.Metal-doped high temperature graphitization carbon gel rubber material has larger specific area, suitable catalyst-loaded central hole structure and good electrical and thermal conductivity performance.Simultaneously, the interpolation of slaine has not only improved the degree of graphitization of high-temperature process material with carbon element, and part is doped in the metal of graphite-structure and the active component acting in conjunction that supports, the activity of raising PEM fuel-cell catalyst and the stability of long-time running.Therefore, when improving metal-doped high temperature graphitization carbon carrier stability, further increase the synergy of carrier and active component, improve the catalytic activity of hydrogen reduction, can improve widely the performance of Proton Exchange Membrane Fuel Cells and the stability of long-time running, break through the bottleneck of Proton Exchange Membrane Fuel Cells commercial applications.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of carbon xerogel, described carbon xerogel can be used as carrier, is used for the fuel battery cathode with proton exchange film catalyst; Prepared carbon xerogel has larger specific area, suitable catalyst-loaded central hole structure and good electrical and thermal conductivity performance, be applied in the fuel battery cathode with proton exchange film catalyst, long-time running corrosion resistance good stability, oxygen reduction reaction activity are high.
For achieving the above object, the technical solution used in the present invention is:
A kind of preparation method of the carbon xerogel as the fuel battery cathode with proton exchange film catalyst carrier, described carbon xerogel, take resorcinol, formaldehyde and slaine as raw material, adopts following process to prepare:
(1) with resorcinol and the solvent ratio in 0.1～10ml solvent/1g resorcinol, mixed dissolution is even, obtains clear solution A;
(2) slaine is joined in above-mentioned solution A, be uniformly mixed, obtain solution B, wherein in resorcinol and slaine, the mol ratio of metallic atom is 10: 1～1500: 1;
(3) in resorcinol and the formaldehyde mole ratio ratio of 1: 1～4: 1, be 20-40wt% formalin to dripping concentration in the solution B in stirring, be uniformly mixed, continue to stir until reaction forms gel C at 20～100 ℃;
(4) gel C is transferred to vacuum drying chamber 60～100 ℃ of lower vacuumize burin-in process 3～12 days, pulverizes and grind after taking out, obtain pressed powder D;
(5) with pressed powder D at inert atmosphere (as: N
2, Ar etc.) in 1600～3500 ℃ of high temperature graphitizations processed 1～10 hour, inert blowing gas is swept to room temperature; Adopt the unreacted slaine of 0.5～5M acid solution eccysis, namely obtain carbon xerogel of the present invention after drying.
Described slaine is the soluble-salt of one or more transition metals in IVB, VB, VIB, VIIB, VIII, IB and IIB family; Described soluble-salt is nitrate, carbonate, sulfate, acetate, halide, dinitroso diamine salts, acetylacetonate or encircles greatly one or more in complex compound porphyrin, the phthalein mountain valley with clumps of trees and bamboo and polymer thereof.
Described transition metal is preferably one or more in Fe, Co, Ni, Cu, Zn, Ir, V, Cr, Mn, Zr, W.
The mol ratio of described resorcinol and formaldehyde is preferably 2: 1, and the mol ratio of resorcinol and slaine is preferably 10: 1～and 500: 1; The graphitization processing temperature of metal organogel is preferably 1600～2800 ℃.
Described acid is nitric acid, hydrochloric acid or sulfuric acid; The mass concentration of described formalin is generally 30～40%; Mass concentration is preferably 37～40%;
Described solvent is one or more in water, ethanol, isopropyl alcohol, ethylene glycol;
When solvent is a kind of in water, ethanol, isopropyl alcohol, ethylene glycol, step 3 wherein) stirring environment for aqueous solvent is 20～80 ℃, it is 20～78 ℃ that alcohol solvent stirs environment, and it is 20～82 ℃ that isopropanol solvent stirs environment, and it is 60～100 ℃ that ethylene glycol solvent stirs environment; Ethanol and isopropyl alcohol have dispersed preferably, and product is uniformly dispersed, and ethylene glycol is applicable to higher temperature environment.
When solvent is a kind of in water, ethanol, isopropyl alcohol; Step 3) stir environment and be preferably 20-50 ℃ of environmental condition gentleness, reduce the solvent evaporates amount, can obtain the gel rubber material of suitable specific area;
Advantage of the present invention is:
1. effect is good.When carbon xerogel is applied on fuel battery cathode with proton exchange film, show higher oxygen reduction reaction activity and long stability.
2. cost of material of the present invention is lower, and technological process is simple, the cycle is short, can, with precursor component charing black lead simultaneously once, can prepare high-specific surface area, the carbon carrier of high stability; In addition, the process conditions of graphitization processing have been relaxed in the slaine doping; Simultaneously, the solvent safety that uses in the carbon xerogel preparation process, nontoxic, environmentally safe.
3. carbon xerogel of the present invention is in the gel-forming process, by what control different amount slaines, adds, regulates precursor solution concentration and reaction environment temperature, can prepare the controllable carbon xerogel material of pore structure and specific area.
4. carbon xerogel of the present invention after high temperature graphitization is processed, has higher degree of graphitization, and stability, higher than common carrier, has suitable pore structure and specific area simultaneously.
5. carbon xerogel of the present invention, by doped metallic elements, has improved the carbon xerogel configuration of surface, has strengthened the adhesion between catalytic active component and carrier, has increased the stability of catalyst.
6. have wide range of applications.As a kind of stability carbon carrier, the active component that the charcoal gel rubber material of high graphitization can support is one or more in precious metals pt, Pt alloy, non-Pt metal and nonmetallic materials.Commercialization process for the catalytic activity that improves non-precious metal catalyst and stability, quickening Proton Exchange Membrane Fuel Cells is significant.
In a word, the present invention has prepared high stability carbon xerogel material by the process of high temperature graphitization, and this material with carbon element has higher stability and hydrogen reduction (ORR) activity while supporting active component as catalyst of fuel batter with proton exchange film; The precursor price of material with carbon element is low; Simultaneously, this carbon support material preparation process is simple, applied range, can be used as the catalyst carrier of different activities component, environmentally safe.
Description of drawings
Fig. 1 is the graph of pore diameter distribution of the Co-CX carrier of 1800 ℃ of graphitization processing of the present invention;
Fig. 2 is the transmission electron microscope photo of the Co-CX carrier of 1800 ℃ of graphitization processing of the present invention;
Fig. 3 is that to prepare content be that 20% Pt/Co-CX catalyst is at 0.5M H to the Co-CX carrier of 1800 ℃ of graphitization processing of the present invention
2SO
4Accelerate the polarization curves of oxygen reduction of decay front and back in solution;
Fig. 4 is that to prepare content be that 20% Pt/Co-CX catalyst is at 0.5M H to the Co-CX carrier of 1500 ℃ of graphitization processing of the present invention
2SO
4Accelerate the polarization curves of oxygen reduction of decay front and back in solution;
Fig. 5 is that the commercialization loading is that 20% Pt/C catalyst is at 0.5M H
2SO
4Accelerate the polarization curves of oxygen reduction of decay front and back in solution;
Fig. 6 accelerates battery performance curve before and after decay for using the Pt/Co-CX of content as 20% of 1800 ℃ of processing of the present invention as the Proton Exchange Membrane Fuel Cells of cathod catalyst; The working temperature of battery is 80 ℃, uses Pt/C as anode catalyst, and anode and cathode pressure is H
2/ O
2=0.2/0.2MPa;
Fig. 7 is that to be 20% Pt/C accelerate performance curve before and after decay as the Proton Exchange Membrane Fuel Cells of cathod catalyst to the commercialization loading; The working temperature of battery is 80 ℃, uses Pt/C as anode catalyst, and anode and cathode pressure is H
2/ O
2=0.2/0.2MPa;
Fig. 8 is that to be 20% Pt/Co-CX accelerate battery performance curve before and after decay as the Proton Exchange Membrane Fuel Cells of cathod catalyst to the content of 800 ℃ of processing of Comparative Examples; The working temperature of battery is 80 ℃, uses Pt/C as anode catalyst, and anode and cathode pressure is H
2/ O
2=0.2/0.2MPa;
Fig. 9 is for using the Pt/Co-CX catalyst of content as 47.6% of 1800 ℃ of processing of the present invention performance curve after as the Proton Exchange Membrane Fuel Cells decay of cathod catalyst; The working temperature of battery is 80 ℃, uses Pt/C as anode catalyst, and Nafion212 is proton exchange membrane, and anode and cathode pressure is H
2/ O
2=0.2/0.2Mpa, air inlet and humidification temperature are H
2/ O
2=90/85 ℃;
Figure 10 is that to be 47.6% Pt/C accelerate performance curve before and after decay as the Proton Exchange Membrane Fuel Cells of cathod catalyst to the commercialization loading; The working temperature of battery is 80 ℃, uses Pt/C as anode catalyst, and Nafion212 is proton exchange membrane, and anode and cathode pressure is H
2/ O
2=0.2/0.2MPa, air inlet and humidification temperature are H
2/ O
2=90/85 ℃.
Embodiment
The present invention is described in detail below by embodiment, but the present invention is not limited only to embodiment.
Embodiment 1
The 6.16g resorcinol is dissolved in the 4mL deionized water, forms clear solution A; Be added drop-wise in above-mentioned clear solution A during the cabaltous nitrate hexahydrate aqueous solution of getting 5.13ml concentration and be 20mg/mL stirs, mix, obtain solution B; Drip 9.08g formalin in the solution B in stirring, further be uniformly mixed, continue to stir in 60 ℃ of environment, until reaction forms gel C; Gel C is transferred to vacuum drying chamber at 80 ℃ of lower vacuumize burin-in process 7d, pulverizes and grind after taking out, obtain pressed powder D; Pressed powder D 1800 ℃ of high temperature graphitizations in N2 are processed 3h, N
2Air-blowing is swept to room temperature, 0.5M H
2SO
4Solution eccysis slaine, obtain resorcinol and the cobalt nitrate mol ratio carbon xerogel support C o-CX of 32: 1.It is 20% Pt/Co-CX1800 catalyst by the standby mass fraction of reduction of ethylene glycol legal system.
As can be seen from Figure 1, the carbon xerogel pore-size distribution concentrates on 3-4nm and 30-100nm.The aperture major part is between the mesopore scope, and specific area is large, meets fuel-cell catalyst and supports demand.
Can find out from Fig. 6 and Fig. 7 contrast, accelerate before and after decay, supported carrier Pt catalyst cell performance of the present invention is all higher than the battery performance of JM company homology module amount commercial catalyst.Wherein, at 1000mA/cm
2Place, carrier Kaolinite Preparation of Catalyst potential decay 39mV of the present invention, JM catalyst decay 63mV.Illustrate that this carrier has corrosion resistance and stability preferably in the fuel cell operation process.
Comparative Examples
The 6.16g resorcinol is dissolved in the 4mL deionized water, forms clear solution A; Be added drop-wise in above-mentioned clear solution A during the cabaltous nitrate hexahydrate aqueous solution of getting 5.13ml concentration and be 20mg/mL stirs, mix, obtain solution B; Drip 9.08g formalin in the solution B in stirring, further be uniformly mixed, continue to stir in 60 ℃ of environment, until reaction forms gel C; Gel C is transferred to vacuum drying chamber at 80 ℃ of lower vacuumize burin-in process 7d, pulverizes and grind after taking out, obtain pressed powder D; With pressed powder D at N
2In 800 ℃ of heat treatment 3h, N
2Air-blowing is swept to room temperature, 0.5M H
2SO
4Solution eccysis slaine, obtain resorcinol and the cobalt nitrate mol ratio carbon xerogel support C o-CX of 32: 1.It is 20% Pt/Co-CX800 catalyst by the standby mass fraction of reduction of ethylene glycol legal system.
In Fig. 8, battery acceleration attenuation test can be found out, the battery performance decay is serious, at 1000mA/cm
2Place, this carrier Kaolinite Preparation of Catalyst potential decay 87mV.Experimental result shows, because treatment temperature does not reach the high graphitization depth, carrier under the highly acid fuel cell operation environment of high potential, less stable, the part corrosion, the catalyst-loaded loss of institute is reunited serious.So high temperature graphitization is processed the raising to the stability corrosion resistance of carrier, has extremely important effect.
The 6.16g resorcinol is dissolved in the 7mL deionized water, forms clear solution A; Get in 0.4355g four hydration cobalt acetate solids stirrings and add in above-mentioned clear solution A, mix and obtain solution B; Drip 9.08g formalin in the solution B in stirring, further be uniformly mixed, continue to stir in 20 ℃ of environment, until reaction forms gel C; Gel C is transferred to vacuum drying chamber at 60 ℃ of lower vacuumize burin-in process 3d, pulverizes and grind after taking out, obtain pressed powder D; With pressed powder D at N
2In 1500 ℃ of high temperature graphitizations process 1h, N
2Air-blowing is swept to room temperature, 2M HNO
3Solution eccysis slaine, obtain resorcinol and the cobalt acetate mol ratio carbon xerogel support C o-CX1500 of 32: 1.It is 20% Pt/Co-CX1500 catalyst by the standby mass fraction of reduction of ethylene glycol legal system.Electrochemistry and battery accelerate the attenuation test result and show, accelerate before and after decay, and Pt/Co-CX1500 catalyst cell performance is all higher than the battery performance of JM company homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 41mV, lower than commercialized catalyst.This shows, this catalyst has activity and stability preferably.
Embodiment 3
The 6.16g resorcinol is dissolved in the 2mL deionized water, forms clear solution A; Get in the stirring of 0.7063g Fe(NO3)39H2O solid and add in above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further be uniformly mixed, continue to stir in 90 ℃ of environment, until reaction forms gel C; Gel C is transferred to vacuum drying chamber at 80 ℃ of lower vacuumize burin-in process 3d, pulverizes and grind after taking out, obtain pressed powder D; Pressed powder D 1900 ℃ of high temperature graphitizations in Ar are processed 5h, and the Ar air-blowing is swept to room temperature, 4M HNO
3Solution eccysis slaine, obtain resorcinol and the ferric nitrate mol ratio carbon xerogel carrier Fe-CX1900 of 32: 1.It is 20% Pt/Fe-CX1900 catalyst by sodium borohydride reduction preparation quality mark.Electrochemistry and battery accelerate the attenuation test result and show, accelerate before and after decay, and Pt/Fe-CX1900 catalyst cell performance is all higher than the battery performance of JM company homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 32mV, lower than commercialized catalyst.This shows, this catalyst has activity and stability preferably.
The 6.16g resorcinol is dissolved in the 10mL deionized water, forms clear solution A; Get in 0.4355g four hydration cobalt acetate solids stirrings and add in above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further be uniformly mixed, continue to stir in 40 ℃ of environment, until reaction forms gel C; Gel C is transferred to vacuum drying chamber at 90 ℃ of lower vacuumize burin-in process 10d, pulverizes and grind after taking out, obtain pressed powder D; Pressed powder D 1800 ℃ of high temperature graphitizations in Ar are processed 8h, and the Ar air-blowing is swept to room temperature, and 3M HCl solution eccysis slaine obtains resorcinol and the cobalt acetate mol ratio carbon xerogel support C o-CX1800 of 32: 1.It is 47.6% Pt/Co-CX1800 catalyst by sodium borohydride reduction preparation quality mark.
Can find out from Fig. 9 and Figure 10 contrast, accelerate before and after decay, the battery performance of supported carrier Pt catalyst of the present invention is all higher than the battery performance of the commercial catalyst of TKK company homology module amount.Wherein, at 1000mA/cm
2Place, carrier Kaolinite Preparation of Catalyst potential decay 31mV of the present invention, TKK catalyst decay 47mV.Illustrate that this carrier has corrosion resistance and stability preferably in the fuel cell operation process.
The 6.16g resorcinol is dissolved in the 7mL deionized water, forms clear solution A; Get in the stirring of 1.6298g cobalt nitrate solid and add in above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further be uniformly mixed, continue to stir in 40 ℃ of environment, until reaction forms gel C; Gel C is transferred to vacuum drying chamber at 70 ℃ of lower vacuumize burin-in process 5d, pulverizes and grind after taking out, obtain pressed powder D; With pressed powder D at N
2In 2200 ℃ of high temperature graphitizations process 10h, N
2Air-blowing is swept to room temperature, and 1M HCl solution eccysis slaine obtains resorcinol and the cobalt nitrate mol ratio carbon xerogel support C o-CX2200 of 10: 1.It is 10% Pt/Co-CX2200 catalyst by hydrogen reduction method preparation quality mark.
Electrochemistry and battery accelerate the attenuation test result and show, accelerate before and after decay, and Pt/Co-CX2200 catalyst cell performance is all higher than the battery performance of homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 28mV, lower than commercialized catalyst.This shows, this catalyst has activity and stability preferably.
Embodiment 6
The 6.16g resorcinol is dissolved in the 7mL deionized water, forms clear solution A; Get in the stirring of 0.1118g hydration Schweinfurt green solid and add in above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further be uniformly mixed, continue to stir in 80 ℃ of environment, until reaction forms gel C; Gel C is transferred to vacuum drying chamber at 85 ℃ of lower vacuumize burin-in process 7d, pulverizes and grind after taking out, obtain pressed powder D; With pressed powder D at N
2In 2700 ℃ of high temperature graphitizations process 10h, N
2Air-blowing is swept to room temperature, 0.5M H
2SO
4Solution eccysis slaine, obtain resorcinol and the Schweinfurt green mol ratio carbon xerogel support C u-CX2700 of 100: 1.It is 50% Pt/Cu-CX2700 catalyst by hydrogen reduction method preparation quality mark.
Electrochemistry and battery accelerate the attenuation test result and show, accelerate before and after decay, and Pt/Cu-CX2700 catalyst cell performance is all higher than the battery performance of homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 21mV, lower than commercialized catalyst.This shows, this catalyst has activity and stability preferably.
Embodiment 7
The 6.16g resorcinol is dissolved in the 20mL deionized water, forms clear solution A; Get in the stirring of 0.1662g Nickel dichloride hexahydrate solid and add in above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further be uniformly mixed, continue to stir in 20 ℃ of environment, until reaction forms gel C; Gel C is transferred to vacuum drying chamber at 60 ℃ of lower vacuumize burin-in process 12d, pulverizes and grind after taking out, obtain pressed powder D; With pressed powder D at N
2In 2200 ℃ of high temperature graphitizations process 3h, the N2 air-blowing is swept to room temperature, 5M HCl solution eccysis slaine obtains resorcinol and the nickel chloride mol ratio carbon xerogel carrier Ni-CX2200 of 80: 1.It is 5% PtCo/Ni-CX2200 catalyst by sodium borohydride reduction preparation quality mark.
Electrochemistry and battery accelerate the attenuation test result and show, accelerate before and after decay, and PtCo/Ni-CX2200 catalyst cell performance is all higher than the battery performance of homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 24mV, lower than commercialized catalyst.This shows, this catalyst has activity and stability preferably.
The 6.16g resorcinol is dissolved in the 10mL deionized water, forms clear solution A; Get in 0.0132g four hydration vanadic sulfate solids stirrings and add in above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further be uniformly mixed, continue to stir in 40 ℃ of environment, until reaction forms gel C; Gel C is transferred to vacuum drying chamber at 90 ℃ of lower vacuumize burin-in process 5d, pulverizes and grind after taking out, obtain pressed powder D; With pressed powder D at N
2In 2800 ℃ of high temperature graphitizations process 3h, N
2Air-blowing is swept to room temperature, and 2M HCl solution eccysis slaine obtains resorcinol and the vanadic sulfate mol ratio carbon xerogel carrier V-CX2800 of 1000: 1.It is 40% Pt/V-CX2800 catalyst by sodium borohydride reduction preparation quality mark.
Electrochemistry and battery accelerate the attenuation test result and show, accelerate before and after decay, and Pt/V-CX2800 catalyst cell performance is all higher than the battery performance of homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 24mV, lower than commercialized catalyst.This shows, this catalyst has activity and stability preferably.
Embodiment 9
The 6.16g resorcinol is dissolved in the 5mL deionized water, forms clear solution A; Get in 0.0555 zinc nitrate hexahydrate solid stirring and add in above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further be uniformly mixed, continue to stir in 30 ℃ of environment, until reaction forms gel C; Gel C is transferred to vacuum drying chamber at 65 ℃ of lower vacuumize burin-in process 8d, pulverizes and grind after taking out, obtain pressed powder D; With pressed powder D at N
2In 1500 ℃ of high temperature graphitizations process 3h, N
2Air-blowing is swept to room temperature, 1M HNO
3Solution eccysis slaine, obtain resorcinol and the zinc nitrate mol ratio carbon xerogel carrier Zn-CX1500 of 300: 1.It is 20% Pt/Zn-CX1500 catalyst by hydrogen reduction method preparation quality mark.
Electrochemistry and battery accelerate the attenuation test result and show, accelerate before and after decay, and Pt/Zn-CX1500 catalyst cell performance is all higher than the battery performance of homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 27mV, lower than commercialized catalyst.This shows, this catalyst has activity and stability preferably.
The 6.16g resorcinol is dissolved in the 15mL deionized water, forms clear solution A; Get in the stirring of 0.4480g Chromium nitrate (Cr(NO3)3),nonahydrate solid and add in above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further be uniformly mixed, continue to stir in 50 ℃ of environment, until reaction forms gel C; Gel C is transferred to vacuum drying chamber at 85 ℃ of lower vacuumize burin-in process 6d, pulverizes and grind after taking out, obtain pressed powder D; With pressed powder D at N
2In 2800 ℃ of high temperature graphitizations process 5h, N
2Air-blowing is swept to room temperature, 0.5M HNO
3Solution eccysis slaine, obtain resorcinol and the chromic nitrate mol ratio carbon xerogel support C r-CX2800 of 50: 1.It is 20% Pt/Cr-CX2800 catalyst by hydrogen reduction method preparation quality mark.
Electrochemistry and battery accelerate the attenuation test result and show, accelerate before and after decay, and Pt/Cr-CX2800 catalyst cell performance is all higher than the battery performance of homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 34mV, lower than commercialized catalyst.This shows, this catalyst has activity and stability preferably.
Embodiment 11
The 6.16g resorcinol is dissolved in the 10mL deionized water, forms clear solution A; Get in 0.0299g two nitric hydrate oxygen zirconium solids stirrings and add in above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further be uniformly mixed, continue to stir in 30 ℃ of environment, until reaction forms gel C; Gel C is transferred to vacuum drying chamber at 85 ℃ of lower vacuumize burin-in process 5d, pulverizes and grind after taking out, obtain pressed powder D; With pressed powder D at N
2In 1600 ℃ of high temperature graphitizations process 4h, N
2Air-blowing is swept to room temperature, 5M H
2SO
4Solution eccysis slaine, obtain resorcinol and the zirconyl nitrate mol ratio carbon xerogel carrier Zr-CX1600 of 500: 1.It is 30% Pt/Zr-CX1600 catalyst by the standby mass fraction of reduction of ethylene glycol legal system.
Electrochemistry and battery accelerate the attenuation test result and show, accelerate before and after decay, and Pt/Zr-CX1600 catalyst cell performance is all higher than the battery performance of homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 35mV, lower than commercialized catalyst.This shows, this catalyst has activity and stability preferably.
Embodiment 12
The 6.16g resorcinol is dissolved in the 5mL deionized water, forms clear solution A; Get in 0.0107g two tungsten oxchloride solids stirrings and add in above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further be uniformly mixed, continue to stir in 20 ℃ of environment, until reaction forms gel C; Gel C is transferred to vacuum drying chamber at 70 ℃ of lower vacuumize burin-in process 7d, pulverizes and grind after taking out, obtain pressed powder D; With pressed powder D at N
2In 2400 ℃ of high temperature graphitizations process 3h, N
2Air-blowing is swept to room temperature, 1M HNO
3Solution eccysis slaine, obtain resorcinol and the two tungsten oxchloride mol ratios carbon xerogel carrier W-CX2400 of 1500: 1.It is 30% Pt/W-CX2400 catalyst by the standby mass fraction of reduction of ethylene glycol legal system.
Electrochemistry and battery accelerate the attenuation test result and show, accelerate before and after decay, and Pt/W-CX2400 catalyst cell performance is all higher than the battery performance of homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 25mV, lower than commercialized catalyst.This shows, this catalyst has activity and stability preferably.
Embodiment 13
The 6.16g resorcinol is dissolved in the 0.1mL deionized water, forms clear solution A; Get in 0.0351g four nitric hydrate manganese solids stirrings and add in above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further be uniformly mixed, continue to stir in 20 ℃ of environment, until reaction forms gel C; Gel C is transferred to vacuum drying chamber at 85 ℃ of lower vacuumize burin-in process 5d, pulverizes and grind after taking out, obtain pressed powder D; With pressed powder D at N
2In 2400 ℃ of high temperature graphitizations process 5h, N
2Air-blowing is swept to room temperature, 1M H
2SO
4Solution eccysis slaine, obtain resorcinol and the manganese nitrate mol ratio carbon xerogel carrier Mn-CX2400 of 400: 1.It is 30% Pt/Mn-CX2400 catalyst by the standby mass fraction of reduction of ethylene glycol legal system.
Electrochemistry and battery accelerate the attenuation test result and show, accelerate before and after decay, and Pt/Mn-CX2400 catalyst cell performance is all higher than the battery performance of homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 18mV, lower than commercialized catalyst.This shows, this catalyst has activity and stability preferably.
The 6.16g resorcinol is dissolved in the 3mL deionized water, forms clear solution A; Get in the stirring of 0.1372g ammonium molybdate solid and add in above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further be uniformly mixed, continue to stir in 20 ℃ of environment, until reaction forms gel C; Gel C is transferred to vacuum drying chamber at 80 ℃ of lower vacuumize burin-in process 7d, pulverizes and grind after taking out, obtain pressed powder D; With pressed powder D at N
2In 2500 ℃ of high temperature graphitizations process 5h, N
2Air-blowing is swept to room temperature, 2M H
2SO
4Solution eccysis slaine, obtain resorcinol and the ammonium molybdate mol ratio carbon xerogel carrier Mo-CX2500 of 80: 1.It is 10% Pt/Mo-CX2500 catalyst by the standby mass fraction of reduction of ethylene glycol legal system.
Electrochemistry and battery accelerate the attenuation test result and show, accelerate before and after decay, and Pt/Mo-CX2500 catalyst cell performance is all higher than the battery performance of homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 16mV, lower than commercialized catalyst.This shows, this catalyst has activity and stability preferably.
Embodiment 15
The 6.16g resorcinol is dissolved in the 10mL deionized water, forms clear solution A; Get in 0.2716g cabaltous nitrate hexahydrate and the stirring of 0.3771g Fe(NO3)39H2O solid and add in above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further be uniformly mixed, continue to stir in 25 ℃ of environment, until reaction forms gel C; Gel C is transferred to vacuum drying chamber at 85 ℃ of lower vacuumize burin-in process 6d, pulverizes and grind after taking out, obtain pressed powder D; With pressed powder D at N
2In 1800 ℃ of high temperature graphitizations process 3h, N
2Air-blowing is swept to room temperature, 2M HNO
3Solution eccysis slaine, obtain the resorcinol cobalt nitrate ferric nitrate mol ratio carbon xerogel support C oFe-CX1800 of 60: 1: 1.It is 50% Pt/CoFe-CX1800 catalyst by the standby mass fraction of reduction of ethylene glycol legal system.
Electrochemistry and battery accelerate the attenuation test result and show, accelerate before and after decay, and Pt/CoFe-CX1800 catalyst cell performance is all higher than the battery performance of homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 29mV, lower than commercialized catalyst.This shows, this catalyst has activity and stability preferably.
Embodiment 16
The 6.16g resorcinol is dissolved in the 8mL deionized water, forms clear solution A; Get in 0.1630g cabaltous nitrate hexahydrate and 0.2787g six hydration nickel acetate solids stirrings and add in above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further be uniformly mixed, continue to stir in 25 ℃ of environment, until reaction forms gel C; Gel C is transferred to vacuum drying chamber at 85 ℃ of lower vacuumize burin-in process 6d, pulverizes and grind after taking out, obtain pressed powder D; With pressed powder D at N
2In 1800 ℃ of high temperature graphitizations process 3h, N
2Air-blowing is swept to room temperature, 2M HNO
3Solution eccysis slaine, obtain the resorcinol cobalt nitrate nickel acetate mol ratio carbon xerogel support C oNi of 100: 1: 2
2-CX1800.Be 50% Pt/CoNi by the standby mass fraction of reduction of ethylene glycol legal system
2-CX1800 catalyst.
Electrochemistry and battery accelerate the attenuation test result and show, accelerate before and after decay Pt/CoNi
2-CX1800 catalyst cell performance is all higher than the battery performance of homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 27mV, lower than commercialized catalyst.This shows, this catalyst has activity and stability preferably.
Embodiment 17
The 6.16g resorcinol is dissolved in the 10mL deionized water, forms clear solution A; Get in 0.0465g four hydration cobalt acetates and the stirring of 0.2029g Gerhardite solid and add in above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further be uniformly mixed, continue to stir in 35 ℃ of environment, until reaction forms gel C; Gel C is transferred to vacuum drying chamber at 85 ℃ of lower vacuumize burin-in process 8d, pulverizes and grind after taking out, obtain pressed powder D; With pressed powder D at N
2In 1600 ℃ of high temperature graphitizations process 3h, N
2Air-blowing is swept to room temperature, 2M HNO
3Solution eccysis slaine, obtain the resorcinol cobalt acetate copper nitrate mol ratio carbon xerogel support C oCu of 200: 1: 3
3-CX1600.Be 20% Pt/CoCu by the standby mass fraction of reduction of ethylene glycol legal system
3-CX1600 catalyst.
Electrochemistry and battery accelerate the attenuation test result and show, accelerate before and after decay Pt/CoCu
3-CX1600 catalyst cell performance is all higher than the battery performance of homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 32mV, lower than commercialized catalyst.This shows, this catalyst has activity and stability preferably.
Embodiment 18
The 6.16g resorcinol is dissolved in the 7mL deionized water, forms clear solution A; Get in 0.4525g Fe(NO3)39H2O and the stirring of 0.1628g Nickelous nitrate hexahydrate solid and add in above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further be uniformly mixed, continue to stir in 25 ℃ of environment, until reaction forms gel C; Gel C is transferred to vacuum drying chamber at 95 ℃ of lower vacuumize burin-in process 6d, pulverizes and grind after taking out, obtain pressed powder D; With pressed powder D at N
2In 1700 ℃ of high temperature graphitizations process 2h, N
2Air-blowing is swept to room temperature, 0.5M HNO
3Solution eccysis slaine, obtain the resorcinol ferric nitrate nickel nitrate mol ratio carbon xerogel carrier Fe of 100: 2: 1
2Ni-CX1700.Be 10% Pt/Fe by the standby mass fraction of reduction of ethylene glycol legal system
2The Ni-CX1700 catalyst.
Electrochemistry and battery accelerate the attenuation test result and show, accelerate before and after decay Pt/Fe
2Ni-CX1700 catalyst cell performance is all higher than the battery performance of homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 33mV, lower than commercialized catalyst.This shows, this catalyst has activity and stability preferably.
Embodiment 19
The 6.16g resorcinol is dissolved in the 10mL deionized water, forms clear solution A; Get in 0.4525g Fe(NO3)39H2O and 0.4490g two nitric hydrate oxygen zirconium solids stirrings and add in above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further be uniformly mixed, continue to stir in 25 ℃ of environment, until reaction forms gel C; Gel C is transferred to vacuum drying chamber at 75 ℃ of lower vacuumize burin-in process 6d, pulverizes and grind after taking out, obtain pressed powder D; With pressed powder D at N
2In 2300 ℃ of high temperature graphitizations process 1h, N
2Air-blowing is swept to room temperature, 0.5M HNO
3Solution eccysis slaine, obtain the resorcinol ferric nitrate zirconyl nitrate mol ratio carbon xerogel carrier Fe of 100: 2: 3
2Zr
3-CX2300.Be 10% Pt/Fe by the standby mass fraction of reduction of ethylene glycol legal system
2Zr
3-CX2300 catalyst.
Electrochemistry and battery accelerate the attenuation test result and show, accelerate before and after decay Pt/Fe
2Zr
3-CX2300 catalyst cell performance is all higher than the battery performance of homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 24mV, lower than commercialized catalyst.This shows, this catalyst has activity and stability preferably.
Embodiment 20
The 6.16g resorcinol is dissolved in the 5mL deionized water, forms clear solution A; Get in 0.2090g nine hydration nickel acetates and 0.0748g two nitric hydrate oxygen zirconium solids stirrings and add in above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further be uniformly mixed, continue to stir in 25 ℃ of environment, until reaction forms gel C; Gel C is transferred to vacuum drying chamber at 95 ℃ of lower vacuumize burin-in process 6d, pulverizes and grind after taking out, obtain pressed powder D; With pressed powder D at N
2In 2700 ℃ of high temperature graphitizations process 1h, N
2Air-blowing is swept to room temperature, 2M HNO
3Solution eccysis slaine, obtain the resorcinol nickel acetate zirconyl nitrate mol ratio carbon xerogel carrier Ni of 200: 3: 1
3Zr
1-CX2700.Be 5% Pt/Ni by the standby mass fraction of reduction of ethylene glycol legal system
3Zr
1-CX2700 catalyst.
Electrochemistry and battery accelerate the attenuation test result and show, accelerate before and after decay Pt/Ni
3Zr
1-CX2700 catalyst cell performance is all higher than the battery performance of homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 19mV, lower than commercialized catalyst.This shows, this catalyst has activity and stability preferably.
Claims (7)
1. the preparation method of a carbon xerogel is characterized in that:
Described carbon xerogel, take resorcinol, formaldehyde and slaine as raw material, adopts following process to prepare:
(1) with resorcinol and the solvent ratio in 0.1～10ml solvent/1g resorcinol, mixed dissolution is even, obtains clear solution A;
(2) slaine is joined in above-mentioned solution A, be uniformly mixed, obtain solution B, wherein in resorcinol and slaine, the mol ratio of metallic atom is 10: 1～1500: 1;
(3) in resorcinol and the formaldehyde mole ratio ratio of 1: 1～4: 1, be 20-40wt% formalin to dripping concentration in the solution B in stirring, be uniformly mixed, continue to stir until reaction forms gel C at 20～100 ℃;
(4) gel C is transferred to vacuum drying chamber 60～100 ℃ of lower vacuumize burin-in process 3～12 days, pulverizes and grind after taking out, obtain pressed powder D;
(5) pressed powder D 1500～3500 ℃ of high temperature graphitizations in inert atmosphere were processed 1～10 hour, inert blowing gas is swept to room temperature; Adopt the unreacted slaine of 0.5～5mol/L acid solution eccysis, namely obtain carbon xerogel after drying;
Described slaine is the soluble-salt of one or more transition metals in IVB, VB, VIB, VIIB, VIII, IB and IIB family.
2. it is characterized in that in accordance with the method for claim 1: described soluble-salt is nitrate, carbonate, sulfate, acetate, halide, dinitroso diamine salts, acetylacetonate or encircles greatly one or more in complex compound porphyrin, the phthalein mountain valley with clumps of trees and bamboo and polymer thereof.
3. it is characterized in that in accordance with the method for claim 1: described transition metal is one or more in Fe, Co, Ni, Cu, Zn, Ir, V, Cr, Mn, Zr, W.
4. in accordance with the method for claim 1, it is characterized in that: the mol ratio of described resorcinol and formaldehyde is 2: 1, and the mol ratio of resorcinol and slaine is 10: 1～500: 1.
5. it is characterized in that in accordance with the method for claim 1: the graphitization processing temperature of pressed powder D is 1500～2800 ℃.
6. it is characterized in that in accordance with the method for claim 1: described acid is nitric acid, hydrochloric acid or sulfuric acid; The concentration of described formalin is 30～40wt%.
7. it is characterized in that in accordance with the method for claim 1: described solvent is one or more in water, ethanol, isopropyl alcohol, ethylene glycol;
When solvent is a kind of in water, ethanol, isopropyl alcohol, ethylene glycol, step 3 wherein) stirring environment for aqueous solvent is 20～80 ℃, it is 20～78 ℃ that alcohol solvent stirs environment, and it is 20～82 ℃ that isopropanol solvent stirs environment, and it is 60～100 ℃ that ethylene glycol solvent stirs environment.
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| CN102856562A (en) * | 2011-06-30 | 2013-01-02 | 中国科学院大连化学物理研究所 | Carbon nanotube doped carbon gel catalyst for fuel cell and its application |
| CN103050702A (en) * | 2011-10-17 | 2013-04-17 | 中国科学院大连化学物理研究所 | Application of carbon material containing in-situ doped component with catalytic activity to lithium-air battery |
| CN103682378B (en) * | 2012-08-30 | 2015-11-18 | 中国科学院大连化学物理研究所 | A kind of fuel cell carbon gels catalyst and application thereof |
| CN103855365B (en) * | 2012-11-28 | 2016-03-16 | 中国科学院大连化学物理研究所 | Lithium-air battery positive pole uses the porous carbon materials of N doping |
| CN103855394B (en) * | 2012-11-28 | 2016-03-23 | 中国科学院大连化学物理研究所 | Lithium-air battery positive pole uses porous carbon materials |
| CN104624157B (en) * | 2015-01-14 | 2017-01-11 | 浙江大学 | High-amino grafted heterogeneous metal doped carbon xerogel as well as preparation method and application thereof |
| CN107039659B (en) * | 2017-04-20 | 2019-12-06 | 沈阳农业大学 | Preparation method of all-vanadium redox flow battery electrode material |
| CN107999023A (en) * | 2017-11-23 | 2018-05-08 | 河南师范大学 | Carry the preparation method of cobalt ordered mesoporous carbon material and its application in Oxone rhodamine B degradation waste water is catalyzed |
| CN111099574A (en) * | 2019-12-27 | 2020-05-05 | 浙江大学 | Preparation method of hierarchical porous carbon aerogel for lithium ion battery cathode |
| CN113644259A (en) * | 2021-06-17 | 2021-11-12 | 上海工程技术大学 | High-activity metal organogel electrode material, and preparation method and application thereof |
| CN114477380B (en) * | 2021-12-29 | 2023-06-23 | 天津科技大学 | Preparation method of functionalized electrode and application of functionalized electrode in photoelectrocatalysis treatment of solubilized organic sewage |
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